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Thermodynamics notes

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Basic Concepts

Introduction:

Thermodynamics deals with heat inter-action and work inter-action with the

substances called systems. Work and heat are forms of energy. Transfer of heat or work

to a substance brings about certain changes in the substance and whatever change

happens is called a process. Thermo means heat. Since work is also a form of energy,

thermo is taken to mean heat and work. Dynamics refers to the changes that occur as a

result of heat or work transfer.

Biological systems are capable doing work. For example, micro-organism is

capable swimming in the body fluid of its host. It needs to do the work. Where does

energy for doing this work come from? It is the metabolic activity that converts some

form of energy (Nutrition that it takes form host is a form of chemical energy) into work.

It is important then to understand how this happens so that we can exploit this to our

engineering benefit.

In thermodynamics we have work transfer, heat transfer and then we have a

system for interaction which undergoes a process. Let us look at these basic terms.

System:

We need to fix our focus of attention in order to understand heat and work

interaction. The body or assemblage or the space on which our attention is focused is

called system. The system may be having real or imaginary boundaries across which the

interaction occurs. The boundary may be rigid and sometimes take different shapes at

different times. If the system has imaginary boundary then we must properly formulate

the idea of system in our mind.

Surroundings:

Every thing else apart from system constitutes surroundings. The idea of

surroundings gets formulated the moment we define system. System and surroundings

together form what is known as universe.

Closed system:

If the system has a boundary through which mass or material cannot be

transferred, but only energy can be transferred is called closed system. In an actual

system, there may not be energy transfer. What is essential for the system to be closed is

the inability of the boundary to transfer mass only.

Open system:

If the system has a boundary through which both energy and mass can transfer, then it is

called open system.

Properties:

Variables such as pressure, temperature, volume and mass are properties. A system will

have a single set of all these values.

Intensive properties:

The properties that are independent of amount contained in the system are called

extensive properties. For example, take temperature. We can have a substance with

varying amount but still same temperature. Density is another example of intensive

property because density of water is same no matter how much is the water. Other

intensive properties are pressure, viscosity, surface tension.

Extensive properties:

The properties that depend upon amount contained in the system are called extensive

properties. Mass depends upon how much substance a system has in it therefore mass is

an extensive property.

State:

It is defined as condition of a system in which there are one set of values for all its

properties. The properties that define the state of a system are called state variables.

There is certain minimum number of intensive properties that requires to be specified in

order to define the state of a system and this number is uniquely related to the kind of

system. This relation is phase rule which we shall discuss little later.

Process:

The changes that occur in the system in moving the system from one state to the other is

called a process. During a process the values of some or all state variables change. The

process may be accompanied by heat or work interaction with the system.

Heat:

It is a form of energy that exists only in transit. This transit occurs between two points

which differ in temperature. Since it exists only in transit, it should be accompanied by

changes that occur in the system. The moment this energy cease to move, it appears as

internal energy. We shall discuss internal energy when we deal with I law of

thermodynamics.

Work:

It is also a form energy that exists only in transit. The work cannot be stored. Work is

defined as the product of force and distance through the force moves. Mathematically,

W f d

f d cos

Let us look at the following piston and cylinder arrangement containing some gas. The

system considered is the gas in the cylinder. It is exerting some pressure on the piston in

the upward direction. This is balanced by the atmospheric pressure plus the weight and

therefore piston though it is free to move, does not move. If the weight is increased, then

dL

the piston moves downwards. The pressure of the gas increases and the movement of the

piston stops when the pressures become equal. The additional weight is doing the work

on the gas. The additional weight has to push the force created by the gas inside to move

the piston. So there is force and distance. But as the piston moves, the pressure

continuously changes. Therefore consider small distance (dL) for which work done (dW)

is also small as shown in the figure which results in small volume change (dV). Then by

definition of work, we have, if A is the cross sectional area of the piston

dW f dL

V

pA d

A

pdV

2

W1 2 pdV

1

This is the equation we use to determine the work. Please note that in general p cannot

be taken out of the integral sign as p may be continuously changing as above.

b

V

If we have a p vs. V curve, we can determine the integral as area under the curve.

The area under the curve a21b is the work done on the gas.

We can carry out a process differently with the same initial and final states given

by the points 1 and 2. Since it is a different process, the curve will be different. In that

case the area under the curve will also be different which means to say the work done is

different though the initial and final states are same. Thus the work depends upon the

process or path or how the state is changing. Such quantities are called path functions.

Since heat is also energy in transit as the work is, heat must also be a path function. No

matter what process, as long we have same initial and final states, it brings about the

same pressure difference. Such properties which depend only on state are called state

properties.

Equilibrium state:

A system is said to be in thermodynamic equilibrium if it satisfies the condition for

thermal equilibrium, mechanical equilibrium and also chemical equilibrium. If it is in

equilibrium, there are no changes occurring or there is no process taking place.

Thermal equilibrium:

There should not be any temperature difference between different regions or locations

within the system. If there are, then there is no way a process of heat transfer does not

take place. Uniformity of temperature throughout the system is the requirement for a

system to be in thermal equilibrium.

Surroundings and the system may be at different temperatures and still system may be in

thermal equilibrium.

Mechanical equilibrium:

There should not be any pressure difference between different regions or locations within

the system. If there are, then there is no way a process of work transfer does not take

place. Uniformity of pressure throughout the system is the requirement for a system to be

in mechanical equilibrium.

Surroundings and the system may be at pressures and still system may be in mechanical

equilibrium.

Chemical equilibrium:

There should not be any chemical reaction taking place anywhere in the system, then it is

said to be in chemical equilibrium. Uniformity of chemical potential throughout the

system is the requirement for a system to be in chemical equilibrium.

Surroundings and the system may have different chemical potential and still system may

be in chemical equilibrium.

Thermodynamic process:

A system in thermodynamic equilibrium is disturbed by imposing some driving force; it

undergoes changes to attain a state of new equilibrium. Whatever is happening to the

system between these two equilibrium state is called a process. It may be represented by a

path which is the locus all the states in between on a p-V diagram as shown in the figure

below.

1

p

2

V

For a system of gas in piston and cylinder arrangement which is in equilibrium, altering

pressure on the piston may be driving force which triggers a process shown above in

which the volume decreases and pressure increases. This happens until the increasing

pressure of the gas equalizes that of the surroundings. If we locate the values of all

intermediate states, we get the path on a p-V diagram.

Phase rule:

The two gas samples below have the same density, viscosity and all other intensive

properties.

1 m3 of nitrogen at a pressure of 2 atmosphere and 300 K

2 m3 of nitrogen at a pressure of 2 atmosphere and 300 K

If a gas behaves ideally, then

pV nRT

n

p

V RT

If M is the molecular weight of the gas, then

m nM pM

V

V

RT

pM

RT

Thus the density of an ideal gas depends upon only temperature and pressure as all other

quantities are constants. Since p and T are same for the above nitrogen samples, density is

same. If we take out 1 cc of sample from any of those two, by observing only this 1 cc

sample we can never from where we took the sample. This means to say the samples are

exactly same and indistinguishable. They are said to be in the same state.

In order to define this state of nitrogen, we need only T and p. Thus we need minimum

two variables to specify the state. This number is given by Gibbs phase rule which is

given by

F 2 N

where

F

: degrees of freedom

: Number of phases

: Number of components

For the above example, number of phases is one; number of components is one therefore

the degrees of freedom are two. For a system containing liquid water and its vapor in

equilibrium, we get the degrees of freedom to be one.

Following is the phase diagram of water which describes in what phase or phases

it can exist for different temperature and temperature.

Liquid

p

Solid

Vapor

T

For the system to have two phases, if we mention the temperature alone given by

the vertical line, the pressure has to be the one given by horizontal line. Given the

pressure, its temperature gets fixed. Thus we have a freedom of fixing only one of them

which amounts to say degrees of freedom is one.

Heat reservoirs:

If the temperature of the system does not change if we remove a finite quantity of heat

from it, then the system is said to be heat reservoir. If the temperature of the system does

not change if we add a finite quantity of heat to it, then the system is said to be heat sink.

Ocean can be made to act either as heat reservoir or heat sink.

Heat Engine:

Work and heat are forms of energy and are inter-convertible. Any device which converts

continuous supply of heat into useful work continuously is called heat engine. For any

system to undergo continuous process, it should be cyclic. The detailed mathematical

treatment of heat engines will follow in 5th chapter on second law of thermodynamics.

Irreversible process:

If a thermodynamic process takes place in such a way that we can retrace the path

exactly, the process is called reversible. Consider a piston and cylinder arrangement with

piston free to move at some pressure and temperature in equilibrium. The pressure of the

gas is balanced by a pressure equal to sum of atmospheric pressure and the weight on the

piston pan as shown. If the weight on the piston is reduced, then the piston moves up. Let

us just displace the part of the weight horizontally. This involves work. The piston moves

up as it is free to move until the pressures again become equal.

State -2

State -1

2

p

V

Looking at the sequencing of the events, it is

1.

2.

Reaching a new steady position called state 2.

1.

2.

Can this reversal be possible? During expansion step, the system does work on the

surroundings. In reverse then, the surroundings should do the work at state 2. This is

not possible as the system and the surroundings have the same pressure. Exact reversing

is not possible. The process of bringing the weight on the piston pan is also not possible

as we need to do only by moving horizontally. The pan level is higher than that of the

weight. This requires extra work to be done. Further, in moving the weight work was

done on the weight. In reverse then, the weight should do the work, go and sit on the pan!

Clearly this is ridiculous which is not possible.

In order for a process to be reversible, the driving force must be infinitesimally small. If

we remove the weight bit by bit and place it horizontally, every bit would be placed one

above the other and then piston moves upward. At any point, the piston and the bit

removed are at the same level. As a result, at any point, we can move the bit horizontally,

making the piston move a bit down where the next bit of weight is available at the same

level. Reversing is thus possible.

However there is one work that can never be reversed even in this process. That is the

work done on the bit to move it horizontally. But this is less irreversible compared to the

earlier process where large part of the weight was removed. Look at the state-2, in order

to reverse; the weight has to be lifted by some vertical distance which is missing in the bit

by bit process. We can only strive to make a process only closer to reversibility.

First law is a statement of law of conservation of energy. For a closed system, since there

is no mass exchange with the surroundings, the total energy of the system must be always

a constant. One form of energy may be converted into another. The system may possess

several forms of energy such as kinetic energy, potential energy, internal energy.

Potential energy:

It is the energy possessed by a body by virtue of its position. An object kept at a height z,

possesses energy to do the work. A spring kept in a compressed state is also capable of

doing work. A body is said to be possessing energy only if it can lift weight by some

mechanical means. If we tie a rope to a body at higher level, pass the rope over a pulley

and tie the other end to another body whose mass is slightly lower, the second body will

be lifted. To one end of the compressed spring in the vertical position, tie a weight and

then release the spring. The weight goes up. Thus a body at higher level or spring in its

compressed state possesses energy. The potential energy of a body of mass m at height of

z from some arbitrary level (reference level) is given by

EP mgz

Arbitrary level may by any level. As long as the same, the changes in energy will also be

same. The changes in potential energy as the level changes will be

EP mg( z f zi ) mgz

Kinetic energy:

It is defined as the energy possessed by a body by virtue of its velocity. For a body of

mass m which is moving with a velocity u, the kinetic energy is given by,

EK

1 2

mu

2

1

1

2

2

EK m(u f ui ) mu 2

2

2

Internal energy:

When some external work is transferred to a body, its temperature increases indicating

rise in internal energy. Internal energy is due to molecular energy of vibration and

rotation.

If Q is the amount of heat transfer to a system which does W amount of work (work

transfer form the system), then the change in the total energy of the system will be Q

W. This change will have its implications on the kinetic, potential and internal energy.

Since law of conservation is to be valid, the change in internal energy Q W must be

equal to the changes occurring in all forms energy. Mathematically,

Q W U EP EK

Generally, the changes in kinetic and potential energy will be negligible compared to heat

and work interaction,

Q W U

This is first law of thermodynamics. Note that Q is the heat transfer to the system and W

is work done by the system.

Cyclic process:

If the process occurs in such a way that periodically its state repeats then the process is

called cyclic process. The following p V diagram represents a cyclic process.

p

1

2

The states 1, 2 and 3 keep repeating in the process in that order. Not only this, all the

states in between also will repeat. Every time process state changes from 1 to 2, 2 to 3

and 3 to 1 following the same paths. During such processes, there will be heat and work

interaction. All the properties will get the same values at state 1 regardless of number of

times cycle repeats. Thus

U1 2 31 V1 2 31 p1 2 31 T1 2 31 0

Since the change in internal energy is zero,

U Q W

Q W 0

Q W

This means that net heat transfer to the system is the net work done by the system.

Cyclic process consists of several steps. In the cyclic process shown in the diagram, there

are three steps viz., 1-2, 2-3 and 3-1.

Let us have another cyclic process for which heat and work interaction are known as

below.

Step

Heat interaction

Work interaction

1-2

No work interaction

2-3

3-1

Net work done by the system, W W2 3 W31 and Q W

Flow processes:

So far we considered closed systems only. Let us look at open systems. Mass exchange

can occur. If the process variables do not change with respect to time for the system, the

process is said to be under steady state conditions. Under such conditions the mass of the

system is constant. This is due to the equality of mass entering and leaving.

If the system as a whole is moving undergoing changes, it constitutes steady state flow

process only when the system at a fixed location will have fixed values.

Heat in, Q

z1

2

z2

Work output, Ws

This diagram shows an open and steady state flow process. The equipment considered is

between 1 and 2. The gas enters at 1 and leaves at 2. Steady state flow process requires

mass entering at 1 is equal to mass leaving at 2. If certain mass of gas considered to be

the system, such as cylindrical shaped gas at 1, when it reaches a particular location such

as A, it will be at a state (having certain fixed values for all the properties). No matter

what time, the system at A will be in the same state. This is true for all locations.

However, state of the system differs from location to location. There is no variation of the

state with respect to time at a given location.

Following is the equipment through which the steam is flowing.

Heat in, Q

z1

2

z2

Work output, Ws

Steam enters at 1 and leaves at 2. There is a heat exchanger which adds heat Q to the

steam making it superheated. The superheated steam runs the turbine and shaft work is

obtained. Thus the gas does the work Ws. The kinetic, potential and internal energy of the

gas changes as it goes from one location to the other. The entrance 1 is at height z1 and

exit is at height z2 from some reference datum. The velocity of the gas varies as the flow

area varies along the path.

Let us consider unit mass of steam whose volume is the volume of cylinder shown at

location 1. This steam element enters the equipment, goes through it receiving heat Q in

the exchanger, doing work at the turbine and comes out at 2.

occurring in potential (as the height at which the steam element is present changes),

kinetic energy (as the velocity changes) and internal energy. Let u1 and u2 be the

velocities at location 1 and 2. Change in kinetic energy, since m =1, is

E K

1 2

2

(u 2 u1 )

2

E P mg( z 2 z1 )

Let the change in internal energy be U . We must account for all heat and work

interaction that occur during the process of steam element moving form 1 to 2. The heat

Q is getting transferred in the heat exchanger to the steam element. Apart from work

output of the turbine, there are other fork forms. At location 1, the surrounding has to do

the work on the steam element to push it into the equipment. If the pressure of the steam

is p1, and the cross sectional area of the pipe is a1, then the distance moved by the steam

element is V1 / a1 where V1 is the specific volume of the steam at 1. The work done at the

entrance on the steam element at 1 is then,

W1 ( p1a1 )

V1

p1V1

a1

Similarly work needs to be done by the steam element at section 2 as it has to push the

surrounding which is given by

W2 ( p2 a2 )

V2

p2V2

a2

The entrance and exit work are also called as flow work. The product of pressure and

volume is the flow work.

If the steam element gets into the equipment, it receives work done by the previous steam

element and uses it to push the element next to it. Thus the net work is zero for all the

locations inside the equipment.

Thus the net work done by the element,

W WS W2 W1

W WS P2V2 P1V1

Substituting in first law of thermodynamics,

Q W E K E P U

Q (WS p 2V2 p1V1 ) E K E P

Q WS E K E P U 2 U 1 p 2V2 p1V1

Q WS E K E P (U 2 p 2V2 ) (U 1 p1V1 )

The group U pV occurs frequently in flow processes and is called enthalpy denoted by

the letter H.

H U pV

Since internal energy, pressure and volume are state functions, enthalpy is also state

function. The above equation becomes,

Q WS E K E P H 2 H 1

Q WS E K E P H

This equation is first law of thermodynamics applied to flow processes. If the changes in

potential and kinetic energy are very small then,

Q WS H

Heat capacity:

Heat capacity of a substance is defined as the heat transfer necessary to bring about a

change in the temperature of unit amount of substance by one degree centigrade. Since it

is heat transfer which is a path function, it depends upon the way heating is done. For

example gases can be heated to increase the temperature by two different methods. The

unit quantity of gas taken in container with rigid wall, when heated its volume remains

constant. Another method is to have the wall which is flexible. If the piston is movable in

the piston and cylinder arrangement, gas when heated pushes piston and pressure will be

constant. Even if we take unit amount of gas in both these heating methods, it is observed

the heat transfer is not the same. Thus we have heat capacity and constant volume and

heat capacity at constant pressure. Mathematically,

dQ

dT

Cp

dQ

dT

CV

dQ

dT V

The heat capacity at constant volume will not be equal to that at constant pressure.

Pressure, temperature and volume of gases vary in a definite manner. Based upon the

conditions, matter can exist in solid, liquid and gas phase. This is represented in graphical

form as below. This diagram is for pure water. All pure substances will have more or less

similar diagrams.

p T diagram for pure water

Fluid

Critical Point.

Liquid

Solid

d

a

Gas

Vapor

T

Based upon the values of pressure and temperature, if the point lies in a region, the

substance will exist in the corresponding state represented. For example the point a

represents solid state and b represents vapor state. Any point lying on the curve

represents both the phases which are in equilibrium. For example, the point d represents

liquid water and its vapor in equilibrium. Thus there are numerous pair of pressure and

temperature values on the curve and all those points represent liquid and vapor in

equilibrium. Each curve will have always two phases in equilibrium.

The point where all the curves meet is called triple point and at this condition, all the

three phase exist in equilibrium. Critical point is the highest temperature and highest

pressure where the liquid and its vapor can exist in equilibrium.

For all pressures and temperatures higher than those at critical point, the liquid and vapor

properties become similar. This state is called fluid.

Phase is considered liquid if it can be vaporized by reduction in pressure keeping T

constant. This is represented by vertical downward arrow in the figure. The initial point is

in liquid phase region. Phase is considered gas if it can be condensed by reduction in T

keeping p constant. This is shown by horizontal arrow pointing towards left. The point a

represents solid state which on increasing the temperature at constant pressure, only the

temperature of the solid increases until it reaches curve where first drop of liquid appears

and beyond this only vapor exists. This is shown as arrow a b.

The other way is representation using p V diagram for pure substance which is given in

the next figure.

S/L

fluid

pC

S

Gas

p

L/V

V

TC

S/V

VC

There are regions where two phases co-exist in equilibrium. The dashed curve labeled Tc

represents an isotherm at critical temperature.

In thermodynamics, we deal largely with either vapor or gases. The significant portion of

the diagram is given below.

fluid

C

pC

L

Gas

p

3

4

V

TC

T1

L/V

VC

constant, the volume decreases along the dashed curve. But this change is very small and

this is why liquids are considered incompressible. Volume change with pressure at

constant temperature is negligible for liquids. Decreasing pressure from 1 at constant

temperature (T1), a point 2 will be reached where first bubble of vapor appears. Any

further attempt to decrease the pressure fails bringing pressure down, instead more and

more liquid becomes vapor and the pressure and temperature remain constant represented

by dashed horizontal line. Thus point such as 3 represent liquid and vapor in equilibrium.

Further attempt in decreasing the pressure brings the state to the point 4 where all the

liquid becomes vapor. Further decrease in pressure at constant will follow the dashed

curve in the gas region. Thus the dashed line represents an isotherm (T1). Given in the

figure there is one more isotherm at a temperature less than T1. The dumb bell shaped

curve represents the locus of all points on all isotherms where the points similar to 2 and

3 lie. The isotherms of higher temperature lie on higher and saturated liquid and vapor

volume become closer and closer and finally merge at the critical point. This is point

where liquid and vapor cannot be distinguished. Isotherm TC has a point of inflexion at

the critical point.

A point on the curve is called point of inflexion if there is a tangent at that point which

lies on either side of the curve as shown below.

which led to lot of research and we have several mathematical equations. All these

equations do have limitations. We will use simple mathematical equation. This is not a

limitation as no matter what equation all it does is relate pressure, temperature and

volume of gases.

pV RT

Internal energy is a function of temperature only.

T2

T2

U CV dT

H C P dT

T1

T1

No matter what process, the changes in internal energy and enthalpy are given by the

above expression not only for ideal gases even for real gases.

This law is valid for low pressures, large volumes and low temperatures.

At constant pressure

dQ

CP

dT p

dQ C P dT ,

At constant volume

dQ

CV

dT V

dQ CV dT ,

Isochoric Process:

Any process in which volume of the system does not change is called isochoric process.

Work done is zero.

U Q W

U Q

T2

U CV dT CV (T2 T1 )

T1

T2

H C P dT C P (T2 T1 ) Q

T1

Isobaric process:

dU dQ pdV

dQ CP dT

dU C P dT pdV

C P (T2 T1 ) p(V2 V1 )

H Q C P (T2 T1 )

W p(V2 V1 )

H U PV

H U RT

dH dU RdT

CP dT CV dT RdT

CP CV R

CP CV R

CP CV

Isothermal Process:

Since the temperature is constant there will not be any change in internal energy.

dU dQ dW

dQ dW

Q W

V2

pdV

V1

V2

pdV

V1

V2

RT

dV

V

V1

p1

p2

p

RT ln 1

p2

RT ln

Q W RT ln

p1V1 p2V2

T1

T2

V2

p

RT ln 1

V1

p2

H U 0

Adiabatic Process:

There will not any heat exchange, Q = 0.

dU dW

RT

dV

V

RT

CV dT

dV

V

dT

R dV

T

CV V

CV dT

CP

R

1

CV

CV

CP

R

1

CV

CV

R

1

CV

dT

dV

( 1)

T

V

dT

dV

( 1)

T

V

T2

2

dT

dV

1

)

T T

V V

1

1

ln

T2

V

( 1) ln 2

T1

V1

V

T

ln 2 ln 1

T1

V2

T2

T1

V

1

V2

The pressure, temperature and volume all vary in the adiabatic process.

Let us get a relation between the other variables.

Since the gas is ideal,

p1V1

pV

2 2

T1

T2

T2 p2V2

T1

p1V1

p2 V1 V1

p1 V2 V2

p1V1 p2V2

pV const

dU dW

T2

U W CV dT

T1

W CV (T2 T1 )

R

(T2 T1 )

1

RT2 RT1

1

p2V2 p1V1

1

p1V1 p2V2

p1 V2

p2 V1

p1V1 p2 p1

W

1

1 p1 p2

V2 p1

V1 p2

p1V1

p2 p2

1 p1 p1

1

1

p1V1 p 2

W

1

1 p1

p1V1 p2

1

1 p1

1 /

p1V1 p2

1

1 p1

1 /

H C P dT

1

2

U CV dT

1

Polytropic Process:

pV n const

Sl. No

Process

1.

Isobaric

2.

Isothermal

3.

Isochoric

.

Guidelines to represent processes on p V diagram:

p

T2

T1

V

In the figure above there are two isotherms shown. For these isotherms, T2 T1. There is

one isotherm passing through every point on p V diagram. Higher the temperature

higher will be location of the isotherm. As they go downwards they converge as shown.

No two isotherms will ever intersect.

Similarly every point has an adiabatic curve passing through it. The adiabatic curve

follows the relation pV const . Thus every point is an intersection of an isotherm and

an adiabatic curve as shown below. The adiabatic curve is steeper.

Adiabatic curve

p

Isotherm

V

No two adiabatic curves will ever intersect.

The mathematical relation between pressure, volume and temperature applicable all

ranges of values has not been possible. However, there are equations which are valid over

certain ranges.

1.

pV RT

As p 0.

2.

p-V curve should have a point of inflexion for isothermal at critical point C,

2 p

p

0 and 2 0

V C

V C

a

p 2 V b RT

V

Here a and b are constants that depend upon the gas. If we apply the partial derivative

conditions, we get,

27 R 2TC

RT

;b C

64 pC

8 pC

The Van der Waals equation is cubic in V. Therefore it should have three roots for a

given set of values of pressure and temperature and for a given substance. For any

temperature higher than critical temperature, there is one positive root. For critical

temperature and critical pressure, all the three roots will be equal which gives critical

volume. For temperature and pressure less than critical values, there will be three roots,

least one gives the molar volume of saturated liquid and highest gives that of saturated

vapor which are volumes given by the two ends of horizontal section of the isotherm.

p

RT

a

V b V (V b) T

a

0.4278R 2TC

pC

5/ 2

;b

0.0867 RTC

pC

Other equations of state are Peng Robinson and Virial equations.

Numerical problem:

Air is compressed from an initial state of 1 bar and 298 K to a final state of 5 bar and 298

K through two mechanically reversible processes in a closed system. First heating at

constant volume followed by cooling at constant pressure. Calculate W, Q, change in

enthalpy and internal energy. Use CP

7R

5R

, CV

.

2

2

2

a

p

Isotherm at 298 K

1

V

The path is shown in the figure. 1 - a represents heating at constant volume and a - 2

represents cooling at constant pressure. Note that initial and final states lie on a single

isotherm.

Let us do the calculations for one mol of gas.

For the path 1 a, since volume is constant, work done is zero.

dU dQ

dU CV dT

Ta

U1 a CV dT

T1

To use this we need to know temperature at a. Since it is closed system and volume is

same at 1 and a,

paTa p1T1

Since pressure at a is same as that at 2,

Ta

1490 K

pa

p2

1

Ta

U1 a CV dT

T1

1490

5R

dT

2

298

5R

(1490 298)

2

5(8.314)

(1490 298)

2

24775.7 J

24.775kJ

1490

H1 a

C dT

P

298

7(8.314)

(1490 298) 34686 J 34.686kJ

2

H1 a U1 a ( pV )1 a U1 a ( paVa p1V1 )

to calculate change in enthalpy.

For the step a 2,

dU dQ dW

T2

U a 2 CV dT

Ta

298

5R

dT

2

1490

5R

(298 1490)

2

24775.7 J

24.775kJ

298

H a 2

C dT

P

1490

7(8.314)

(298 1490) 34686 J 34.686kJ

2

dW pdV

Wa 2 pdV

a

2

Wa 2 pdV

a

5x105 (V2 Va )

From gas law, at the initial condition, V1

8.314(198)

0.02477m3

5

1x10

p2V2 p1V1

T2

T1

The temperatures are equal,

V2

p1V1

p2

1(0.02477)

5

0.004954m3

Similarly,

Va

RTa 8.314(1498)

0.1245m3

pa

1x105

Since the volume is decreasing, work is done on the system.

U a 2 Qa 2 Wa 2

24.775 Qa 2 (59.773)

Qa 2 84.548kJ

For the entire process,

U1 2 U1 a U a 2 24.775 24.775 0

H1 2 H1 a H a 2 34.686 34.686 0

W1 2 W1 a Wa 2 0 (59.773) 59.773kJ

Since there are no changes in internal energy and enthalpy, work done on the system is

given out as heat.

No matter what is the process the internal energy and enthalpy are determined using the

following formulae.

dU CV dT

dH CP dT

If the process is isochoric, then dU CV dT dQ.

If the process is isobaric, then dH CP dT dQ.

Let us recall that

1.

For ideal gases internal energy is a function of temperature only.

2.

The change in internal energy is a state function.

Let us take an adiabatic process and determine change in internal energy.

2

p

1

V

Consider two states (1) and (2) on an adiabatic path. There is one isotherm for each state

as shown. Adiabatic curve at (1) is steeper than the isotherm. Whether the process

follows adiabatic path or another curve shown in the figure or any arbitrary path, as long

the initial and final state are same, we get the same change in internal energy.

2

p

1

V

Let us replace adiabatic path by two steps

1.

2.

a 2 isothermal process

U12 U1a U a 2

Since step 1 a is a constant volume process, dU CV dT will have to be used. The step

a 2 is isothermal and therefore dU = 0.

Ta

U12 CV dT 0

T1

Since Ta T2 ,

T2

U12 CV dT

T1

Any process between any two states can be replaced by either an isothermal process

followed by constant volume process or constant volume process followed by an

isothermal process. The total change in internal energy is the change in internal energy

for constant volume step only. Thus no matter what process the change in internal energy

is given by dU CV dT .

The deviation from ideal behavior is measured using what is known as

compressibility factor defined as the ratio of volume determined using ideal gas law

to the actual volume at any given temperature and pressure.

Vactual pV

Videal RT

For ideal gases, Z = 1. Higher the value Z away from one higher will be the non-ideality.

Following figure gives the value of Z as a function pressure for different gases. All gases

approach ideal gas behavior at low pressures. This figure is called compressibility chart.

There will be as many curves as there are number of gases. The chart that is given here is

for one temperature. Therefore this figure becomes highly cumbersome if applied for all

gases and all temperatures.

N2

CH4

1.0

Z

C2H6

p

Theory of corresponding states:

It states that all fluids, when compared at the same reduced temperature and reduced

pressure, will have same compressibility factor and all deviate from ideal behavior to the

same extent.

The reduced pressure and temperature are defined by

pr

Tr

p

pC

T

TC

Tr 1.5

Tr 2.5

Z

Tr 1.0

pr

Here all gases with the same reduced temperature and pressure lie on the same curve.

This chart is called generalized compressibility chart. Different gases are indicated by

different points on the curve. There will be as many curves as there are temperatures.

This is less cumbersome compared to compressibility chart.

N2

CH4

Tc

189.

3

286.0

83.7

5

114.

126.

2

190.

p

c

pr

33.

5

45.

r

1.

5

1.

2.

5

2.

The above table gives two gases with the same Z for different T and p. The reason is that

the critical values are different.

It is defined as the enthalpy change accompanying a reaction when both reactants and

products are at their standard states at 298 K and is denoted by H 0 298 .

2C( s ) O2 ( g ) 2CO( g )

H 0 298 221.2 kJ

C( s )

1

O2 ( g ) CO( g )

2

Then,

H 0 298

221.2 kJ

110.6 kJ

2

The standard heat of combustion of a substance is defined as the enthalpy change

accompanying the reaction when one mol of the substance undergoes combustion when

both reactants and products are at 298K.

H 0 298 2336.24kJ

The heat of combustion is 1168.12 kJ.

Standard heat of formation of a substance is defined as the change in enthalpy

accompanying the formation of 1 mol of the substance from the constituent elements

when the reactants and products are at 298K.

2C( s ) O2 ( g ) 2CO( g )

H 0 298 221.2 kJ

110.6 kJ .

The net enthalpy involved in a reaction is the same whether the reaction takes place in a

single step or in a series of steps.

A B C

Let A and B react to form C with heat of reaction H. Let there be one more method of

carrying out this reaction in two steps as given below.

A B AB

AB C

H1

H 2

A B C ,

It has been found that

H1 H 2

H1 H 2 is same as H .

This idea is used to determine heat of reaction from heat of formation or heat of

combustion data.

For example if we want to determine heat of formation of sulfuric acid, we must

determine this from the reaction,

H 2 S 2O2 H 2 SO4

No matter what we do, the above reaction cannot be carried out. Let us carry out other

possible reactions such that the over-all reaction is the formation reaction as below.

S O2 SO2

2 SO2 O2 2 SO3

H1 ----------(1)

H 2 ----------(2)

SO3 H 2 O H 2 SO4

H2

1

O2 H 2 O

2

H 3 -----------(3)

H 4 ----------(4)

2 S 2O2 2 SO2

2 SO2 O2 2 SO3

2 H1 ----------(1)

H 2 ----------(2)

2 SO3 2 H 2 O 2 H 2 SO4

2 H 2 O2 2 H 2 O

2 H 3 -----------(3)

2 H 4 ----------(4)

2 H 2 2 S 4O2 2 H 2 SO4

and heat of this reaction will be 2( H1 H 3 H 4 ) H 2

Therefore heat of formation of sulfuric acid is H1 H 3 H 4

H 2

2

This is how Hesss law can be used to determine the heat of reaction of a reaction from

heat of reaction of other reactions.

First deals with law of conservation of energy and defines internal energy.

A stone falls decreasing its potential energy and converting it into kinetic energy. Just

before it strikes the ground, it has maximum kinetic energy. From there why does it not

go up decreasing its kinetic energy and converting it into potential energy?

If we keep two bodies at different temperature in contact, why there is no heat transfer

from a body of low temperature to a body at higher temperature?

When we remove the wall which separates two gases, the two gases mix together without

any external work done on them. Why then the two gases in a mixed state separate

themselves without any external work?

For all the processes mentioned above there is absolutely no violation of I law. In spite of

that, we do not observe these processes. It appears that there is some sense of direction

for spontaneous processes. There is nothing in the first law to indicate any such direction

to any process.

Is there any difference between heat and work though they are both forms of energy? If

they inter-convertible, then any cyclic process should be able to convert all the heat

supplied into work completely as change in internal energy is zero. Does it happen? It has

been found that we cannot have a device whose sole effect is conversion of heat supplied

into work completely. Let us look at why this is so with an example of a process.

In the following figure, there is a heat exchanger where heat is supplied (Q1) to the

system which is water in this case and generates steam at high pressure. The steam flows

into a turbine and rotates it producing useful work WS. From the turbine, we get steam at

relatively lower pressure than with which it entered. The objective here is to convert heat

Q1 into work. Since this heat is available, can we send the steam from turbine directly

into the heat exchanger in order to make it work continuously so that we get continuous

supply of work? This is shown by a dotted arrow.

The moment we establish this connection, whole process comes to an abrupt stop! We

have lower pressure steam line going into the heat exchanger in which there is higher

pressure steam. If there is connection like this, why does steam preferentially go into the

turbine line? It will enter into both the lines and stop the turbine. Therefore, in order to

have this going on, we must condense the steam bring about a change in its state so that it

can be fed to the heat exchanger. This state must be same as that of feed water to the heat

exchanger.

Turbine

WS

Heat Exchanger

Q1

Condenser

Q2

completely into work. The work obtained Ws is less than Q1 by an amount equal to Q2.

By first law, since for a cycle change in internal energy is zero,

WS Q1 Q2

Practically Q2 cannot be zero.

If we analyze any cyclic process, there will be several heat and work interactions, such

that net work done is equal to net heat supplied. There will be always one step in which

there is heat removed which brings down the amount of heat that is getting converted into

work.

This fact is the basis of statement of II law of thermodynamics. There are several

statements for the II law which are equivalent. In fact we can deduce one from any other.

All the statements are given below.

1.

2.

accompanied by degradation of energy.

3.

to produce no effect other than

4.

continuously to produce no effect other than transfer of heat from low

temperature body to a high temperature body.

The Carnot cycle consists of four steps and all the four steps are reversible. The cycle is

shown in the diagram below.

TH

TC

B

D

There are two isotherms and two adiabatic processes as shown. The isotherms are at TH

and TC.

AB Reversible isothermal expansion

BC Reversible adiabatic expansion

CD Reversible isothermal compression

DA Reversible adiabatic compression

According to first law, it can be shown that

pA

pB

WBC CV ( TH TC )

pC

pD

WDA CV ( TC TH )

The net work done is given by

RTH ln

p

pA

CV ( TH TC ) RTC ln C CV ( TC TH )

pB

pD

TH pB

TC pC

( 1 ) /

TC pD

TH pA

( 1 ) /

pD pA

pC pB

Net work done becomes,

Wnet R( TH TC ) ln

pA

pB

QAB W AB RTH ln

pA

pB

Wnet

QAB

R( TH TC ) ln

RTH ln

pA

pB

pA

pB

TH TC

TH

It is clear that efficiency of Carnot engine depends upon only the temperatures between

which it is operating and not on the working substance undergoing the cycle. Since

Carnot engine is reversible, it must have maximum efficiency.

Q

T

1 CD 1 C

QAB

QAB

QAB

TH

1

QCD

T

1 C

QAB

TH

QCD TC

QAB TH

Let QCD is heat removed, and be equal to QC; and heat added as QH, with sign

convention,

QC TC

which can be simplified to

QH

TH

QH QC

0

TH TC

This equation is applicable to the complete cycle and any quantity that adds to zero for

the cycle is a state property. Thus Q/T is a state property called entropy. Thus second law

of thermodynamics brings in the idea of entropy.

Efficiency of engines:

The efficiency of reversible Carnot Engine is given by

QH QC TH TC

QH

TH

The maximum efficiency of any engine operated between two temperatures is always

given by

TH TC

TH

Efficiency of real engine is always less than that of reversible engine. If the engine is

irreversible then efficiency is calculated from

QH QC

QH

dQH dQC TH TC

dQH

TH

dQC TC

dQH

TH

dQC dQH

TC

TH

Applying sign convention,

dQC dQH

0

TC

TH

dQ

0

T

dQ

0

T

dQ

0

T

In general,

This is called Clausius inequality. The sum of dQ / T terms over a cycle is less than or

equal to zero depending upon whether the cycle is irreversible or reversible.

The changes in entropy are always determined using,

dS

dQRe v

T

1

p

Let A1B Represent irreversible process and A2B represent reversible process between

the same states.

dS

dQRe v

T

SAB

dQ

T

A2 B

dQ

T

A1B

To determine entropy change we must have only reversible path. However the entropy

change between the states 1 and 2 is same regardless of the path as it is a state function.

What the above equation says is entropy is not equal to dQ/T along an irreversible path.

To determine entropy change for any irreversible path between two states, replace the

path by a reversible path with the same states, and find the entropy of the reversible path.

Let us look at a cyclic process given below.

1

p

Let A1B Represent reversible process and B2A represent irreversible process between

the same states. Therefore A2B is also irreversible. Since A1B is reversible,

SA1B

dQ

T

A1B

dQ

0

T

dQ

dQ

0

T

T

A1B

B2 A

SA1B

dQ

0

T

B2 A

SB 2 A

dQ

0

T

B2 A

dQ

SB 2 A

T

B2 A

LHS is dQ / T term and it is along an irreversible path and therefore it does not represent

entropy change.

For a process involving transfer of heat Q from heat source at T1 to a heat sink at T2,

( S )total

Q Q

T1 T2

T T2

( S )total Q 1

T1T2

The process can be made less and less irreversible by lowering the temperature T1 closer

and closer to T2.

As the temperatures become closer and closer, irreversibility decreases and Stotal 0.

For any heat transfer there has to be some temperature difference. Therefore T1 > T2 and

hence,

Stotal 0.

This is the mathematical statement of II law of thermodynamics. Thus the entropy of the

universe always increases and the energy is conserved.

Because of irreversibility, there will be some dissipation and degradation of energy which

will not be available as work. This is called lost work which is given by

Wlost T0 Stotal

Where T0 refers to the temperature of the sink to which heat is rejected.

dS

dQR

T

This is the basic equation. The heat transfer term may replaced by any term using first

law or any equation applicable to the process for which entropy change is to be

determined. This is applicable only the process is reversible. For example, for an ideal

gas undergoing isothermal reversible process,

dQ dW pdV

pdV

dS

T

RdV

dS

V

V

S R ln 2

V1

This is how entropy changes may be determined

Apart from enthalpy, internal energy and entropy, there are other thermodynamic

properties which are necessary to apply to phase equilibria and reaction equilibria. So far

we have treated only closed systems which consist of single phase without any reaction.

In order treat the systems we need to know other energy terms involved with reaction and

phase equilibria. The use these properties will get clearer when we do the chapters on

these areas.

Enthalpy:

From I law,

dU dQ dW

dU TdS pdV

H U pV

dH dU d(pV)

dU pdV Vdp

TdS pdV pdV Vdp

dH TdS Vdp

It is defined as

A = U TS

Differentiating,

dA = dU-d(TS)

= TdS pdV TdS SdT

dA= - pdV SdT

Gibbs Free energy:

It is defined as G = H TS

Differentiating, dG= dH TdS SdT

= TdS +Vdp TdS SdT

dG = Vdp - SdT

These four equations are called fundamental property relations as many equations are

derived from these equations.

Maxwells relations

As some of the thermodynamic properties are not directly measurable, we must write the

equations in terms of measurable properties. The measurable and determinable (by

experiment) properties are temperature, pressure, volume, heat capacities and in some

cases even enthalpies. These relations are derived from fundamental property relations.

The derivations are based upon a mathematical relation applied to exact differential

equations.

f

f

If z = f(x,y) then df dx dy

x y

y x

df = Mdx + Ndy

For this differential equation to be exact,

M

x x y

df Mdx Ndy

x x y

dU TdS pdV

T

p

V S

S V

dH TdS Vdp

T V

p S S p

dA pdV SdT

p

S

T V V T

dG Vdp SdT

S

V

T p

p T

Generating function:

Consider

G

d

RT

RTdG Gd( RT )

R 2T 2

1

G

dG

dT

RT

RT 2

1

H TS

( Vdp SdT )

dT

2

RT

RT

RT

RT

RT 2

RT

V

H

dp

dT

RT

RT 2

G

d

RT

H

V

dp

dT

RT 2

RT

From this equation, at constant temperature and at constant pressure we can write,

( G / RT

( G / RT

)

V

RT ;

T

)

H

RT

p

2

thermodynamic properties and hence it is called generating function.

Entropy changes:

Q

Q

We know that CP

; CV

T p

T V

Since dQ TdS ,

S

CP T

T p

C

S

P

T p T

And

S

CV T

T V

C

S

V

T V T

Using these,

T2

S p CP

T1

T2

T

dT

CP ln 2 and

T

T1

S V CV

T1

T

dT

CV ln 2

T

T1

If S is considered as

S = f (T,p) then

S

S

dS

dT dp

T p

p T

In this equation, the first partial derivative is replaced by CP/T which is derived and

second by a Maxwells relation, we get,

dS

CP

V

dT

dp

T

T p

dS

CV

p

dT

dV

T

T V

If there is any relation between three variables, from mathematics we have, a relation

between p, V and T as

V

p T

1

T T V V p

dS

( V / T )p

CV

dT

dV

T

( V / p )T

( V / T )p

dU CV dT T

p dV

( V / p )T

dU CP dT T

dp pdV

T p

V

dH CP dT V T

dp

T p

The internal energy changes can be expressed in terms measurable quantities such as heat

capacities, pressure, volume and temperature. We can use Maxwells relations to get

these expressions.

The following are fundamental property relations.

dU TdS pdV

dH TdS Vdp

dA pdV SdT

dG Vdp SdT

We have derived the following relations.

dS

dS

dS

CP

V

dT

dp

T

T p

CV

p

dT

dV

T

T V

( V / T )p

CV

dT

dV

T

( V / p )T

p T

1

T T V V p

Let us derive the expression for internal energy in terms CP and CV.

dU TdS pdV

( V / T )p

C

dU T V dT

dV pdV

( V / p )T

T

( V / T )p

dU CV dT T

p dV

(

V

/

p

)

T

dU TdS pdV

C

V

dU T P dT

dp pdV

T p

T

V

dU CP dT T

dp pdV

T p

Enthalpy changes:

Starting from

dH TdS Vdp

in the same way we can get,

V

dH CP dT V T

dp

T p

We can use these expressions and find the changes in enthalpy. These equations are

applicable for any gas. P-V-T relations used should be for the gas for which you are

determining the changes.

Use these relations and derive the expressions for dH and dU for ideal gas.

S

V

T p

p T

This is one of the Maxwells relations which gives the effect of pressure on entropy at

constant temperature.

C

S

P

T

T p

This equation derived earlier gives the effect of temperature on entropy at constant

pressure.

( V / T )p

dU CV dT Vdp T

dV

( V / p )T

At constant volume,

Or

dU

CV

dT

U

CV

T V

( V / T )p

U

p

T

V T

( V / p )T

Similarly from

V

dH CP dT V T

dp

T p

we can get,

At constant pressure, H CP

T p

At constant temperature,

H

V

V T

T p

p T

The heat capacities are related by the following expression.

V p

CP CV T

T p T V

2

V p

CP CV T

T p V T

1 V

;

V T p

1

V

are called Volume expansivity and isothermal Compressibility. The difference between

heat capacities is written in terms of these as

CP CV

2VT

These are given by the following equations.

CP

2V

T

T 2

T

2V

CP

T

2

V T

T

p

V

T

p

2 p

CV

T

2

T

V T

CV

2 p V

T

T 2 p

T

is given by

V

RT

c

p T3

Cp a bT

Derive the expressions for changes in internal energy, enthalpy and entropy for an

isobaric process.

V

dU CP dT T

dp pdV

T p

As pressure is constant, dp = 0,

Internal energy:

dU CP dT pdV

dU ( a bT )dT pdV

U12 a( T2 T1 )

Enthalpy:

b

( T2 2 T1 2 ) p( V2 V1 )

2

V

dH CP dT V T

dp

T p

dH CP dT

H12 a( T2 T1 )

dS

Entropy:

b

( T2 2 T12 )

2

CP

V

dT

dp

T

T p

dS

CP

dT

T

a bT

dS

dT

T

S1 2 a ln

T2

b( T2 T1 )

T1

A perfect gas is heated from 60 to 300oC at a constant pressure of 4 bar. The gas is then

cooled to 60oC at constant volume. The mass of the gas is 5 kg. Determine total entropy

change. CP and CV are 1.0 and 0.72 kJ/kg.K

pressure

T1

T2

3

volume

T2

S1 2

T1

T2

T1

dQ

T

C p dT

T

ln

576

0.5479kJ / kg.K

333

T3

S2 3

T2

dQ

T3

T2

CV dT

333

0.72 ln

0.3945kJ / kg.K

576

T

S13 S12 S2 3

S1 3 0.5479 0.3945

0.2161kJ / kg.K

Prove that

dU ( Cp pV )dT V ( p T )dp

Where

1

V

V

1 V

V T p

p T

U U(T , p )

U

U

dp

dU

dT

p

p T

dU TdS pdV

U

S

V

T

p

T p

T p

T p

dS

dQ

T

dS

C p dT

T

Cp

S

T

T

Cp

V

U

p

T

T

p

T p

dU TdS pdV

U

S

V

T

p

p T

p T

p T

S

V

T p

p T

U

V

V

p

T p

p T

p T

Cp

dU T

T

V

V

p

dp

dT

T p

T p

p T

V

V

V

dp

C p p

dT T

p

T p

T p

p T

( Cp pV )dT ( TV pV )dp

dU ( Cp pV )dT V ( p T )dp

U

U

U

0

p T V T S T

dU TdS pdV

U

V

T p

T

S T

T

U

T p

S T

p V

pV

R

T

V

p V R

V

U

T p 0

S

R

T

dU TdS pdV

U

S

T

p

V T

V T

p

S

T V V T

U

p

T

p

T

T V

H U pV

U H pV

V

U

H

p

V

T

T

T

H

V

V T

T p

p T

U

V V

V T

p

T p p

p T

V

T

U

V

V

p

T p

p T

p T

U

R

RT

T p 2 0

p

p

p

And hence

U

U

U

V

T S T

Fugacity

It is derived from Latin, expressed as fleetness or escaping tendency. It is used to study

extensively phase and chemical reaction equilibrium.

We know that

dG VdP SdT -(1)

For isothermal condition

dG VdP

For ideal gases

RT

P

RT

.dP

P

dG RTd ln P

dG

pressure. Which we call fugacity(f).

dG RTd ln f -------(2)

Applicable for all gases (ideal or real)

On differentiation

G RT ln f

Is an constant depends on temperature and nature of gas.

fugacity has same units as pressure for an ideal gas.

For ideal Gases

dG VdP SdT

For Isothermal conditions

dG VdP

from equation (2)

RTd ln f VdP

V

d ln f

dP

RT

dp

p

d ln f d ln p

f p

Fugacity = Pressure for Ideal gases

d ln f

component to its pressure.

f

P

Is the measure of non ideal behavior of the gas.

Standard State: Pure gases, solids and liquids at temperature of 298k at 1 atmosphere are

said to exist at standard condition. The property at this condition are known as standard

state property and is denoted by subscripto.

f o = Standard fugacity

I method

dG VdP SdT

For Isothermal conditions

dG VdP

from equation (2)

RTd ln f VdP

V

d ln f

dP

RT

Integrating the above equation with the limits 0 to f and pressure 1 to P

d ln f RT dP

1

At 1 atm assuming the gases expected to behave ideally

1

VdP

RT 1

if PVT relations are known , we can find fugacity at any temperature and pressure

ln f

II method

Using compressibility factor

dG VdP

RTd ln f VdP --------------(2)

V in terms of compressibility terms it is given as V

ZRT

P

Substitute V in equation 2

ZRT

RTd ln f

dP

p

d ln f Zd ln p

subtracting both sides by dlnP

d ln f d ln P Zd ln P d ln P

d ln

f

( z 1)d ln P

P

d ln (Z 1)d ln P

Integrating the equation from 1 to and 0 to P

d ln (Z 1)d ln P

1

ln ( Z 1)

0

dP

P

Using generalized charts: using reduced properties a similar chart as compressibility chart

is predicted for fugacity.

f

Z 1

ln

dPr

P

Pr

Using Residual Volume(): The residual volume is the difference between actual

volume (V) and the volume occupied by one mole of gas under same temperature and

RT

RT

pressure V

, V

P

P

RT

dG

dP RTd ln f

P

dP

RT

dP

RTd ln f

P

RT

f

dP d ln

RT

P

ln

dP

P

RT

Problem

Z=1- 9.86 x 10-3P-11.45 x 10-5P2

Where P is in bars. Estimate the fugacity at 50 bars and 200 oC

PV

Z

1 9.86 10 3 P 11.41 10 5 P 2

RT

ZRT RT

(1 9.86 10 3 P 11.41 10 5 P 2 )

p

P

P

1

ln f

VdP

RT 1

1

ln f

RT

50

ln f

RT

(1 9.86 10 3 P 11.41 10 5 P 2 )dP

P

50

50

dp

3

5

1 p 1 9.86 10 dP 1 11.41 10 PdP

2

2

50

3

5 (50 1 )

ln f ln 9.86 10 50 1 11.41 10

2

1

f=26.744 bar

f 26.744

0.5348

P

50

General expression for fugacity is

P

1

ln f

VdP

RT 1

For solids and liquids at constant temperature the specific volume does not change

appreciably with pressure, therefore the above equation is integrated by taking volume

constant. Integrating the above equation from condition 1 to 2

f2

P

V 2

ln

f

f

P dP

RT

1

1

ln

f2

V

P2 P1

f1 RT

Problem:

Liquid chlorine at 25oC has a vapour pressure of 0.77Mpa, fugacity 0.7Mpa and Molar

volume 5.1x 10-2 m3/kg mole. What is the fugacity at 10 Mpa and 25oC

P1 0.77 10 6 Pa

f1 0.7 10 6 Pa

P2 10 10 6 Pa

ln

T 298K R 8314

J

Kgmole

f2

V

P2 P1

f1 RT

f=0.846Mpa

Activity(a):

It is defined as the fugacity of the existing condition to the standard state fugacity

f

a o

f

Effect of pressure on activity

The change in Gibbs free energy for a process accompanying change of state from

standard state at given condition at constant temperature can be predicted as

G RT ln f

G o RT ln f o

f

G G G o RT ln o RT ln a

f

at constant temperature dG VdP

GO

dG V dP

Po

G V ( P P o ) RT ln a V ( P P o )

ln a

V

( P P o ) This equation predicts the effect of pressure on activity

RT

G G G o RT ln a

G Go

T

T

Differentiating the above equation with T at constant P

Go

G

T

T

d ln a

T

dT P T

P

P

o

H

H

d ln a

R

2

RT

RT 2

dT P

R ln a

Ho H

d ln a

This equation predicts the effect of temperature on activity.

R

RT 2

dT P

Properties of solutions

The relationships for pure component are not applicable to solutions. Which needs

modification because of the change in thermodynamic properties of solution. The

pressure temperature and amount of various constituents determines an extensive state.

The pressure, temperature and composition determine intensive state of a system.

The properties of a solution are not additive properties, it means volume of solution is not

the sum of pure components volume. When a substance becomes a part of a solution it

looses its identity but it still contributes to the property of the solution.

The term partial molar property is used to designate the component property when it is

admixture with one or more component solution.

A mole of component i is a particular solution at specified temperature and pressure has

got a set of properties associated with it like VP , S i etc . These properties are partially

responsible for the properties of solution and it is known as partial molar property

It is defined as

nM

Mi

ji

n

i

T , P ,n

j

M = Any thermodynamic property of the solution

n = Total number moles in a solution

ni=Number of moles of component I in the solution

This equation defines how the solution property is distributed among the components.

Thus the partial molar properties can be treated exactly as if they represented the molar

property of component in the solution.

The above expression is applicable only for an extensive property using

We can write

nM ni M i

M xi M i

ni

xi

n

Measuring of partial molar properties

To understand the meaning of physical molar properties consider a open beaker

containing huge volume of water in one mole of water is added to it, the volume increase

is 18x 10-6 m3 If the same amount of water is added to pure ethanol the volume increased

is approximately 14 x 10 -6m3 this is the partial molar volume of H2O in pure ethanol.

The difference in volume can explain the volume applied by water molecules depending

on water molecules surrounding to them. When water is added to large amount of

ethanol, ethanol molecules hence volume occupied surround all the water molecules will

be different in ethanol.

volume change will be different. Therefore Partial molar property change with

composition. The intermolecular forces also changes with change in thermodynamic

property.

Let Vw = Partial molar volume of the water in ethanol water solution

V t =Total volume of solution when water added to ethanol water mixture and allowed

for sufficient time so that the temperature remains constant

V t n w Vw

Vw

V t

n w

In a process a finite quantity of water is added which causes finite change in composition.

Vw = property of solution for all infinitely small amount of water.

Vw lim v0

V t V t

nw nw

water.

V t

Vw

nE- no of moles of ethanol

nw T , P ,n

E

V t

Vi

ni T , P ,n i

j

Consider any thermodynamic extensive property (Vi, Gi etc) for homogenous system can

be determined by knowing the temperature, pressure and various amount of constituents.

Let total property of the solution

M t nM

n n1 n2 n3

1,2,3 represents no of constituents

Thermodynamic property is a f T , P, n1 , n2 , n3 n j

For small change in the pressure and temperature and amount of various constituents can

be written as

M t

M t

M t

M t

dM t

dP

dT

dn

dni

1

P T ,n

P p ,n

P T , p ,n ,n

P P ,T ,n i

2

The above equation reduces to

M t

dM

dni

i 1 ni P.T , n

j i

dMt in terms of partial molar property

i n

dM t M i dni

i 1

All constituent properties at constant temperature and pressure are added to give the

property of the solution.

dM t M 1dn1 M 2 dn2 M 3 dn3

dM t M 1 x1 M 2 x2 M 3 x3 dn

M M 1 x1 M 2 x2 M 3 x3 n M 1n1 M 2 n 2 M 3 n 3

t

M t ni M i

Problem

A 30% mole by methanol water solution is to be prepared. How many m3 of pure

methanol (molar volume =40.7x10 -3 m3/mol) and pure water (molar volume =

18.068x10-6 m3/mol) are to be mixed to prepare 2m3 of desired solution. The partial molar

volume of methanol and water in 30% solution are 38.36x10 -6 m3/mol and 17.765x10 -6

m3/mol respectively.

Methanol =0.3 mole fraction

Water=0.7 mole fraction

Vt=0.3 x38.36x10-6+0.7x17.765x10-6

=24.025x10-6 m3/mol

For 2 m3soolution

2

83.246 10 3 mol

6

24.025 10

Number of moles of methanol in 2m3solution

Number of moles of water in 2m3solution

=83.246x103x07= 58.272x103mol

Volume of pure methanol to be taken

= 24.97x103 x 40.7x10-3 =1.0717 m3

Volume of pure water to be taken

= 58.272x103 x 18.068x10-6 =1.0529 m3

Two methods for estimation

Analytical Method and Graphical Method(Tangent Intercept method)

Analytical Method: The general relation between partial molar property and molar

property of the solution is given by

M

M i M x k

k i x1

x K T , P ,n

k

i 1, k 2

M 1 M x 2

x2 x1 1, x2 1 x1 , x2 x1

x 2 T , P

At constant Temperature and pressure

M

M 1 M (1 x1 )

x1

M

M 2 M x1

x1

------(a)

-----------(b)

The partial molar property (extensive property) for a binary mixture can be estimated

from the property of solution using above equations (a) and (b).

This is the graphical method to estimate partial molar properties. If the partial molar

property (M) is plotted against the composition we get the curve as shown in the figure.

Suppose partial molar properties of components required at any composition, and then

draw a tangent to this point to the curve. The intercept of the tangent with two axis x 1=1

and x1=0 are I1 and I2.

Slope of the tangent

M I 2 x1

dM

dx1

I 2 M x1

dM

dx1

dM M I 2

dx1

x1

I 1 M 1 x1

dM I 1 M

dx1

1 x1

dM

dx1

I 1 M 1 x1

dM

Comparing with equation(a) I 1 M 1

dx1

Limiting cases: For infinite dilution of component when at x1=0 a tangent is drawn at

x1=0 will give the partial molar property of component 1 at infinite dilution ( M 1 ) and

M2

Problem

The Gibbs free energy of a binary solution is given by

cal

mol

(a) Finnd the partial molar free energies of the components at x2=0.8 and also at infinite

dilution.

(b) Find the pure component properties

cal

mol

G 9 x1 8x1 49 x1 150

3

G1 G (1 x1 )

x1

G

2

27 x1 16 x1 49

x1

G1 18x1 35x1 16 x1 101

3

G2 G x1

x1

3

x2=0.8,

x1=1-0.8 = 0.2

3

G1 102.944

cal

mol

3

G2 149.824

cal

mol

At infinite dilution

G1 G1atx1 0

G1 101

G2

G2

cal

mol

G2 atx1 1 or x2=0

160

cal

mol

G1 G1atx1 1

G1 100

cal

mol

G2 G2 atx1 0

G1 150

cal

mol

Chemical Potential:

It is widely used as a thermodynamic property. It is used as a index in chemical

equilibrium, same as pressure and temperature. The chemical potential i of component i

in a solution is same as its partial molar free energy in the solution G i

The chemical potential of component i

G t

i Gi

ni T , P ,n

G t f P, T , n1 , n2

i n

G t

G t

G t

dG

dni

dP

dT

i 1 ni T ,n

P T ,n

T P ,n

j

t

G t

G t

dG t

dP

dT i dni

P T ,n

T P ,n

dG t V t dP S t dT

at constant temperature

G

t

P V

T

at constant pressure

G

t

T S

P

dG t V t dP S t dT i dni

dG

t

T ,P

i dni

Effect of temperature:

We know that

G t

i Gi

-------------------(1)

ni T , P ,n

j

2G

i

T Tdn ---------------------(2)

P ,n

i

G

T S

P

differentiating again w r t ni

S t

2G

Si

Tni

ni P ,n j

S i is partial molar entropy of component I

i

T

T

T i i

T2

P ,n

T Si i

T2

G H TS

Gi H i T S i

i H i T S i

H i i T S i

Hi

i

T

T2

P ,n

Effect of Pressure:

We know that

G t

i Gi

-------------------(4)

ni T , P ,n

j

2G

i

P Pdn ---------------------(5)

T ,n

i

G

P V

T

differentiating again w r t ni

V

2G

Vi ,

Pni ni T ,n

j

i

P Vi

T ,n

This equation represents the effect of pressure on chemical potential

Fugacity in solutions

For pure fluids fugacity is explained as

dG RTd ln f

lim P0

f

1

P

d i RTd ln f i

limP 0

Pi

i is Chemical potential

f i is partial molar fugacity

For ideal gases Pi yi PT

PT Total pressure.

We know that

G t

i Gi

------(1)

ni T , P ,n

j

2G

i

-----(2)

T ,n Pdn i

G

P V

T

differentiating again w r t ni

V

2G

Vi ,

Pni ni T ,n

j

i

P Vi

T ,n

i Vi P

RTd ln f i Vi dP

Vi

dP

RT

Subtracting both sides by d ln Pi

d ln f i

d ln f i d ln P i

Vi

dP d ln P i

RT

f V

d ln i i dP d ln P i

Pi RT

d ln Pi d ln P d ln yi

The above equation can be written as

dP

P

d ln Pi d ln P

d ln i

1

RT

RT

V i

P

dP

Ideal solutions

An ideal mixture is one, which there is no change in volume due to mixing. In other

words for an ideal gaseous mixture partial molar volume of each component will be equal

to its pure component volume at same temperature and pressure.

and V Vi xi xiVi --- Raoults law

Ideal solutins are formed when similar components or adjacent groups of group are

mixed

Eg: Benzene-Toluene

Methanol- Ethanol

Hexane- Heptane

Solutin undergo change in volume due to mixing are known as non ideal solutions

Vi Vi

Eg: Methanol-Water

Ethanol-water.

Ideal solutions formed when the intermolecular force between like molecules and unlike

molecules are of the same magnitude.

Non-ideal solutions are formed when intermolecular forces between like molecules and

unlike molecules of different magnitude.

For ideal solutions

V t niVi -------------------(1)

Vi is the molar volume of pure component I

V t

Vi

T , P , n j Vi ----------------- (2)

n

i

RT

Vi

p

P

f

1

RT

ln i

Vi

dP ----(3)

P RT 0

P

For component i in terms of partial molar properties

P

f

1

RT

ln i

V i

dP ----(4)

P

Pi RT 0

Subtracting equation (3) from (4)

fi P

1

ln

f i Pi RT

V

P

Vi dP ----(5)

we know that Pi yi P

equation (5) reduces to

P

fi

1

ln

V i Vi dP

f i yi RT 0

fi

1

f i yi

f i f i yi --Lewis Randal rule

Lewis Randal rule is applicable for evaluating fugacity of components in gas mixture.

Lewis Randal rule is valid for

1. At low pressure when gas behaves ideally.

2. When Physical properties are nearly same.

3. At any pressure if component present in exess.

Henrys Law

This law is applicable for small concentration ranges. For ideal solution Henrys law is

given as

f i xi k i

Pi xi k i

ki- Henrys Constant, f i -Partial molar fugacity,

Pi -Partial pressure of component i.

For ideal solutions f i xi k i ------------(a)

Where i is an activity coefficient of component i.

Comparing equation (a) and (b)

f

i i Non ideal solution / Ideal solution

fi

For both ideal and Non ideal solutions the fugacity of solution is given by

equation

f

ln f xi ln i

xi

ln xi ln i

Problem:

A terinary gas mixture contains 20mole% A 35mole% B and 45mole% C at 60 atm and

75oC. The fugacity coefficients of A,B and C in this mixture are 0.7,, 0.6 and 0.9.

Calculate the fugacity of the mixture.

Solution:

ln x A ln A x B ln B xc ln c

ln 0.2975

0.7426

f

,

P

f =44.558atm

Consider a multi component solution having ni moles of component I the property of

solution be M in terms of partial molar properties

M t nM n M i -----------------------(1).

Where n is the total no of moles of solution

Differentiating eq (1) we get

d (nm) ni d M i M i dni ----------------------------(2)

We know that

nM f T , P, n1 , n2

(nM )

(nM )

(nM )

(nM )

(nM )

dT

dP

dn1

dn2

T P ,n1 ,n2

P T ,n1 ,n2

n1 T , P1 ,n2.n3

n2 T , P ,n1 ,n3

(nM )

n( M )

n( M )

(nM )

dT

dP

dni

P

T P , n1 , n2

T , n1 , n2

ni T , P , n j

From the definition of partial molar properties

n( M )

n( M )

(nM )

dT

dP M i dni

P

T P ,n1 ,n2

T ,n1 ,n2

----------(3)

n( M )

n( M )

dT

dP ni d M i 0 ------------------(4)

T

P T ,n1 ,n2

P ,n1 , n2

Equatin (4) is the fundamental form of Gibbs Duhem equation

Special Case

At constant temperature and pressure dT and dP are equal to zero. The equation becomes

xi d M i 0

For binary solution at constant temperature and pressure the equation becomes

x1d M 1 x2 d M 2 0

x1d M 1 (1 x1 )d M 2 0 ------------(5)

x1

d M1

dM2

(1 x1 )

0

dx1

dx1

The above equation is Gibbs Duhem equation for binary solution at constant temperature

and pressure in terms of Partial molar properties.

Any Data or equation on Partial molar properties must satisfy Gibbs Duhem

equation.

Problem:

Find weather the equation given below is thermodynamically consistent

G 100 x1 150 x2 x1 x2 (10 x1 x2 )

G1 G (1 x1 )

G2 G x1

G

x1

G

x1

3

3

d G1

dx1

54 x1 70 x1 16

2

d G2

2

54 x1 16 x1

dx1

G D equation

x1

d M1

dM2

(1 x1 )

0

dx1

dx1

x 1 ( 54 x 1 70 x 1 16 ) ( 1 x1 )( 54 x 1 16 x 1 ) 0

2

Phase Equilibrium

Criteria for phase equilibrium: If a system says to be in thermodynamic equilibrium,

Temperature, pressure must be constant and there should not be any mass transfer.

The different criteria for phase equilibrium are

At Constant U and V: An isolated system do not exchange mass or heat or work with

surroundings. Therefore dQ=0, dW=0 hence dU=0. A perfectly insulated vessel at

constant volume dU=0 and dV=0.

dSU ,V 0

At Constant T and V: Helmoltz free energy is given by the expression

A U TS

U A TS

on differentiating

dU dA TdS SdT

we know that

dU TdS PdV

TdS PdV dA TdS SdT

dA PdV SdT

Under the restriction of constant temperature and volume the equation simplifies to

dAT ,V 0

At Constant P and T

The equation defines Gibbs free energy

G H TS

G U PV TS

dG dU PdV VdP TdS SdT

dU dG PdV VdP TdS SdT

dU dG dG PdV TdS

Under the restriction of constant Pressure and Temperature the equation simplifies to

dGT , P 0

This means the Gibbs free energy decreases or remains un altered depending on the

reversibility and the irreversibility of the process. It implies that for a system at

equilibrium at given temperature and pressure the free energy must be minimum.

Consider a thermodynamic equilibrium system consisting of two or more phases of a

single substance. Though the individual phases can exchange mass with each other.

Consider equilibrium between vapor and liquid phases for a single substance at constant

temperature and pressure. Appling the criteria of equilibrium

dG 0

dG a dG b 0

dG a and dG b are chane in free energies of the phases a and b respectively.

We know that

dG VdP SdT Gi dni

For phase a

dG a V a dP a S a dT a G a dn a

For phase b

dG b V b dP b S b dT b G b dn b

dG a G a dn a , dG b G b dn b

For a whole system to be at equilibrium

dn a dn b 0

or

dn a dn b

G b dn a 0

Ga Gb

When two phases are in equilibrium at constant temperature and pressure, Gibbs free

energies must be same in each phase for equilibrium.

RT ln f a C RT ln f b C

fa fb

Clapeyron Clausius Equation are developed two phases when they are in equilibrium

(a) Solid- liquid

(b) Liquid-Vapor

(c) Solid Vapor

Consider any two phases are in equilibrium with each other at given temperature and

pressure. It is possible to transfer some amount of substance from one phase to other

in a thermodynamically reversible manner(infinitely slow).The equal amount of

substance will have same free energies at equilibrium .

Consider GA is Gibbs free energy in phase A and GB is Gibbs free energy in phase B

at equilibrium.

GA=GB ------(1)

G = GA -GB =0 ------(2)

At new temperature and pressure the free energy / mole of substance in phase A is

G A dG A for Phase B G B dG B

From basic equation

dG VdP SdT -----(3)

dG A V A dP S A dT

dG B VB dP S B dT

V A dP S A dT VB dP S B dT

dPVB V A dT S B S A

dP S

dT V

V represents the change in volume when one mole of substance pases from

phase A to Phase B

Q

S

T

dP

Q

dT TV

dP

Q

----(4)

dT T V B V A

This is a basic equation of Clapeyorn Clasius equation.

BVapor state A- Liquid state

Q=molar heat of vaporization = H V

VB is molar volume in vapor state, VA is molar volume in liquid state,

dP

Q

dT T V g Vl

dP H V

dT TV g

RT

P

dP

P

dT TRT

dP dT

P

RT2

Integrating the above equation from T1to T2 and pressure from P1 to P2.

dP 2 dT

P P R T T

1

1

P2

P 1

1

ln 2

P1 R T1 T2

This equation is used to calculate the vapor pressure at any desired temperature.

Problem:

The vapor pressure of water at 100oC is 760mmHg. What will be the vapor pressure

at 95oC. The latent heat of vaporization of water at this temperature range is

41.27KJ/mole.

P1 760 mmHg T1 100 273 373 K

P2

T2 95 273 368 K

P 1

1

ln 2

P1 R T1 T2

P 41.27 10 3

ln 2

8.314

760

1

1

373 368

P2 634.3mmHg

An heterogeneous system contains two or more phases and each phase contains two or

more components in different proportions. Therefore it is necessary to develop phase

equilibrium for multi component system in terms of chemical potential.

The partial molar free energy or chemical potential is given as

G

i Gi

ni T , P ,n

j

For a system to be in equilibrium with respect to mass transfer the driving force for

mass transfer( Chemical potential) must have uniform values for each component in

all phases.

, , and

containing various components 1,2,3-------C , that constitutes the system.

k

The symbol i represents chemical potential of component iin phase k.

At constant temperature and pressure, for the criterion for equilibrium is

dG=0 ----(1)

Free energy for multi component system given by the expression

dG VdP SdT i dni ------(2)

At constant Temperature and pressure

dG i dni ----(3)

Comparing equation 1 and 3

0 i dni

For multi component system

C

i 1 k

k

i

dni 0

k

1 dn1 1 dn1 1 dn1 1 dn1

-----(4)

Since the whole system is closed it should satisfy the mass conservation equation

----(5)

The variation in number of moles dni is independent of each other. However the sum of

change in mole in all the phases must be zero. For the criterion of equilibrium is that the

chemical potential of each component must be equal in all phases.

1 1 1

2 2 2

C C C

At constant temperature and pressure the general criterion for thermodynamic

equilibrium in closed system for heterogeneous multi component system

At constant T and P

i

i

for i=1,2,3--------C

Since i Gi RT ln f i

The above equation is also satisfied in terms of fugacity

fi fi fi

for i=1,2,3--------C

Constant pressure equilibrium

Consider a Binary system made up of component A and B. Where it is assumed to be

more volatile than B where vapour pressure A is more than B. When the pressure is

fixed at the liquid composition can be changed the properities such as temperature and

vapour compositions get quickly determined VLE at constant pressure is represented on

T-xy diagram.

Boiling point diagrams

When temperature is plotted against liquid(x) and vapour(y) phase composition. The

upper curve gives and lower curve gives. The lower curve is called as bubble point

curve and upper curve is called as Dew point curve. The mixture below bubble point is

sub cooled liquid and above the Dew point is super heated vapour. The region between

bubble point and Dew point is called mixture of liquid and vapour phase.

point A. When the mixture is heated slowly temperature rises and reach to point B,

where the liquid starts boiling, temperature at that point is called boiling point of whether

heating mixture reaches to point G when all liquids converts to vapour the temperature

at that point is called as Dew point. Further heating results in super heated vapour. The

number of tic lies connects between vapour and liquid phase. For a solution the term

boiling point has no meaning because temperature varies from boiling point to Dew point

at constant pressure.

The boiling point diagram is drawn from composition x=0 to x=1, boiling point of pure

substances increases with increase in pressure. The variation of boiling point diagrams

with pressure is as shown in diagram. The high pressure diagrams are above low

pressure.

Equilibrium diagram

Vapor composition is drawn against liquid comp at constant pressure. Vapour is always

rich in more volatile component the curve lies above the diagonal line.

VLE diagram is drawn against composition at constant temperature. The upper curve is

and lower curve is drawn at vapour comp(y). Consider a liquid at known pressure and

composition at point A as the pressure is decreases and reaches to point B where it

starts boiling further decreases in pressure reaches to point C when all the liquid

converts to vapour, further decreases in pressure leads to formation of super heated

vapour. In between B to C both liquid and vapour exists together

An ideal solution obeys Raoults law and p-x line will be straight. Non ideal solution do

not obey Raoults law. The total pressure for non ideal solutions may be greater or lower

than that for ideal solution. When total pressure is greater than pressure given by Raoults

law, the system shows positive deviation from Raoults law.

Eg: Ethanol-toluene

When the total pressure at equilibrium is less than the pressure given by Roults law the

system shows negative deviation from Raoults law.

Eg: Tetrahydrofuron-ccl4

Azeotropes

Azeotropes are constant boiling mixtures. When the deviation from Raoults law is very

large p-x and p-y curve meets at this point y1=x1 and y2=x2

A mixture of this composition is known as Azeotrope. Azeotrope is a vapour liquid

equilibrium mixture having the same composition in both the phases.

Types of Azeotropes

Azeotropes are classified into two types

1. Maximum curve pressure, minimum boiling azeotropes

2. Minimum pressure maximum boiling azeotrope

The azeotrope formed when negative deviation is very large will exhibit minimum

pressure or maximum boiling point, this is known as minimum pressure Azeotrope.

Eg : Ethanol water, benzene-ethanol

The azeotrope formed when ue deviation is very large will exhibit minimum pressure or

maximum boiling point, this is known as minimum pressure azeotrope.

Phase diagram for both types of Azeotropes

Minimum Temperature azeotropes

Ideal solution: Ideal solution is one which obeys Raoults law. Raoults law states that the

partial pressure is equal to product of vapor pressure and mole fraction in liquid phase.

PA PVA x A

PA- Partial pressure

xA- Mole fraction of component A

For binary solution (For component A and B)

We know that PT PA PB -------(1)

PA PVA x A , PB PVB x B

Substitute PA and PB in equation 1

PT PVA x A PVB x B

1 x A xB , 1 x A xB

PT PVA x A PVB (1 x A )

PT PVA PVB x A PVB --------(2)

P PVB

xA T

PVA PVB

Assuming the vapor phase is also ideal

PA PVA x A

PT

PT

Substituting PT from equation (2)

yA

yA

PVA x A

PVA PVB x A PVB

PVA

xA

PVB

yA

PVA

1 x A 1

PVB

yA

x A

1x A 1

is known as relative volatility of component A with respect to component B

Problem: The binary system acetone and acetone nitrile form an ideal solution. Using

the following data prepare

P-x-y diagram at 50oC

T-x-y diagram at 400mm Hg

x-y diagram at 400 mm Hg

T

38.45

42

46

50

54

58

62.3

PV1

400

458.3

532

615

707.9

811.8

937.4

PV2

159.4

184.6

216.8

253.5

295.2

342.3

400

Solution: PT PV 1 PV 2 x1 PV 2 , y A

x1

0.0

0.2

0.4

0.6

0.8

1.0

PT

253.5

325.8

398.1

470.4

542.7

615

PV 1 x1

, PV1= 615, PV2 = 253.5

PT

y1

0.0

0.377

0.6179

0.784

0.906

1

T

PV1

PV2

x1

38.45 400

159.4

1

42

458.3

184.6

0.7869

46

532

216.8

0.5812

50

615

253.5

0.405

54

707.9

295.2

0.2539

58

811.8

342.3

0.122

62.3 937.4

400

0

Calculation of VLE for non Ideal solution

PT PV 2

P x

, y A V1 1

PV 1 PV 2

PT

y1

1

0.9015

0.7729

0.6226

0.449

0.2475

0

Partial pressure is given by Pi i xi PVi

i - Activity coefficient

PVi vapor pressure

For binary mixture

P1 1 x1 PV 1

P2 2 x2 PV 2

PT P1 P2

PT 1 x1 PV 1 2 x2 PV 2

1 x1 PV 1

P1

PT 1 x1 PV 1 2 x 2 PV 2

1

x P

1 2 2 V2

1 x1 PV 1

The above equation relates x and y for non ideal solution

y1

Activity coefficients are functions of liquid composition x, many equations are available

to estimate them. The important equations are

Vanlaar equation

Wilson equation

Margules Equation

Vanlaar Equation:

Estimation of activity coefficient

2

Ax 2

ln 1

2

A

x

2

B 1

ln 2

Bx1

x1 A x 2

Where A and b are known as vanlaar constants, if the constants are known the

activity coefficients can be estimated.

Estimation of Vanlaar constants

1st Method: If the activity coefficients are known at any one composition, then vanlaar

constants A and B can be estimated by rearranging the equation

x ln 2

A ln 1 1 2

x1 ln 1

x ln 1

B ln 2 1 1

x 2 ln 2

2nd Method

For a systems forming azeotrope, if the temperature and pressure s are known at

azeotropic composition then activity coefficients can be calculated as shown below.

P1 x1 1 PV 1

PT y1 x1 1 PV 1

At azeotrpic composition x1=y1

PT

PT

1,

2

PV 1

PV 2

Van laar constants A and B can calculated using the above equations.

Problem: The azeotope of ethanol and benzene has composition of 44.8mol% C2H5OH at

68oC and 760mmHg.At 68oC the vapor pressure of benzene and ethanol are 517 and 506

mmHg.

Calculate

Vanlaar constants

Prepare the graph of activity coefficients Vs composition

Assuming the ratio of vapor pressure remains constant, prepare equilibrium

diagram at 760mmHg.

Solution:

At azeotropic composition x1=y1=0.448,

PV2 =517mmHg

PT

1,

PV 1

x2=y2=0.552,

PV1=506mmHg,

PT

2

PV 2

760

1 1.501 ,

506

x ln 2

A ln 1 1 2

x1 ln 1

760

2 1.47

517

2

(0.552) ln(1.47)

A ln(1.501) 1

(0.448) ln(1.501)

A=0.829

x ln 1

B ln 2 1 1

x 2 ln 2

(0.448) ln(1.501)

B ln(1.47) 1

(0.552) ln(1.47)

B=0.576

Make use of the equations given below for plotting graph of activity coefficients Vs

composition.

ln 1

y1

Ax 2

B x1 x 2

, ln 2

1 x1 PV 1

P1

PT 1 x1 PV 1 2 x 2 PV 2

x1

0

0.2

0.4

0.6

0.8

1.0

x2

1

0.8

0.6

0.4

0.2

0

Bx1

x1 A x 2

1

x P

1 2 2 V2

1 x1 PV 1

6.745

2.4

1.644

1.21

1.0112

1

1

1.095

1.374

1.721

2.618

3.723

y1

0

0.384

0.4384

0.5077

0.609

1

Margules equation

Eetimation of activity coefficients

2

ln 1 x2 A 2B Ax1

ln 2 x1 B 2A Bx2

2

The constant A in the above equation is terminal value of ln1 at x1=0 and constant B is

the terminal value of ln2 at x2=0

When A=B

2

2

ln 1 Ax 2 , ln 2 Ax1

The above equations are known as Margules suffix equation.

Wilson Equation:

Wilson proposed the following equation for activity coefficients in binary solution

12

21

ln 1 lnx1 12 x2 x2

x1 12 x2 21 x1 x2

12

21

ln 2 lnx2 21 x1 x1

x1 12 x2 21 x1 x2

Wilson equation have two adjustable parameters 12 and 21 . These are related to pure

component molar volumes.

12

V2

11 V2

a

exp 12

exp 12

V1

RT V1

RT

V1

22 V1

a

exp 12

exp 21

V2

RT V2

RT

V1 and V2 molar volumes of pure liquids

- Energies of interaction between molecule

Wilson equation suffers main disadvantages which is not suitable for maxima or minima

on ln versus x curves.

Consistency of VLE data

Gibbs duhem equation in terms of thermal consistency

21

x1

d ln 1

d ln 2

(1 x1 )

0

dx1

dx1

According to Gibbs Duhem equation both slopes must have oppsite sign then only the

data is consistent, otherwise it is inconsistent.

For the data to be consistent it has satisfy the following condition.

1. If one of ln curves has maximum at certain concentration and the other curve

should be minimum at same composition.

2. If there is no maximum or minimum point both must have + ue or ue on entire

range.

Co-existence equation

The general form of Gibbs duhem equation at constant temperature and pressure

xi d M i 0 ---(1)

In terms of partial molar free energies

xi d Gi 0 ------(2)

dividing equation (2) by dx1

d Gi

0 -----(3)

dx1

Gi RT ln f i

at constant temperature

d Gi RT ln f i

----(4)

dx1

dx1

substituting equation (4) in equation (3)

x

x

RT ln f i

0

dx1

d ln f i

0 ------(5)

dx1

d ln f1

d ln f 2

x1

x2

0 ----(6)

dx1

dx1

x1d ln f1 x2 d ln f 2 0 -----(7)

Equation (5) (6) and (7) are Gibbs Duhem equation in terms of fugacites and thus

applicable for both liquid and vapor phase

For liquids

f i i xi f i

ln f i ln i ln xi ln f i

=0

d ln f i d ln i d ln xi d ln f i

-------(8)

dx1

dx1

dx1

dx1

Substituting equation (8) in equation (5)

d ln

d ln x

xi dx i xi dx i 0

1

1

=0

d ln i

0 ----------------(9)

dx1

d ln 1

d ln 2

x1

x2

0 ---------(10)

dx1

dx1

x1d ln 1 x2 d ln 2 0 -----------(11)

Equation (9) (10) and (11) are Gibbs Duhem equation in terms of activity coefficients

For ideal vapor

f i Pi

From equation 5

d ln Pi

0 ------------(13)

dx1

For binary system

x1

d ln P1

d ln P2

x2

0 ----------(14)

dx1

dx1

x1d ln P1 x2 d ln P2 0 ---------------(15)

Equation (13) (14) and (15) are Gibbs Duhem equation in terms Partial pressure.

For ideal vapor

P1 y1 PT , P2 y 2 PT

x1d ln( y1 PT ) x2 d ln( y2 PT ) 0

x1d ln y1 x1d ln y2 ( x1 x2 )d ln PT 0

x1 x2 1

x1d ln y1 x1d ln y 2 d ln PT 0

dP

x1 d ln y1 x2 d ln y 2

P

dy

dy

dP

x1 1 x2 2

P

y1

y2

y 2 y1 0 , dy 2 dy1

on simplification

x (1 x1 )

dP

dy1 1

P

(1 y1 )

y1

Further simplification

y x

dP

P 1 1

dy1

y (1 y1 )

This is known as coexistence equation. It relates P,x,y for binary VLE system. This

equation is used to rest consistency of VLE data.

x1d ln 1 x2 d ln 2 0

d ln 2

x1 d ln 1

x2

d ln 2

x1 d ln 1

(1 x1 )

d ln 2

x1 d ln 1

(1 x1 )

The excess free energy of mixing for a solution is given as

G e Gideal GNonideal

G e RT xi ln i

G e RT x1 ln 1 x2 ln 2

differentiating with respect to x1

d ln 1

d ln 2

dx

dG e

RT x1

ln 1 x2

ln 2 2

dx1

dx1

dx1

dx1

d ln 1

d ln 2

x1

x2

0

dx1

dx1

dx

dG e

RT ln 1 ln 2 2

dx1

dx1

dx2 dx1

dG e

RT ln 1 ln 2

dx1

dG e

RT ln 1

dx1

2

x1 1

dG

x1 0

RT

x1 1

1

ln dx1

2

x1 0

The two limits indicates pure component for which G e 0 , where LHS is zero for both

limits.

We can write

x1 1

0 ln 1 dx1

2

x1 0

This can be checked graphically. Net area should be equal to zero for

consistency(Area=0).

Problem

Verify whether the following data is consistent

X1

0

0.2

0.4

0.6

0.8

1.0

Solution:

1

0.576

0.655

0.748

0.856

0.950

1.00

2

1.00

0.985

0.930

0.814

0.626

0.379

x1 1

0 ln 1 dx1

2

x1 0

1

2

1

2

ln

0.576

0.665

0.804

1.052

1.518

2.639

-0.552

-0.408

-0.218

0.051

0.417

0.97

Plot ln

1

Vs x1

2

\

Area under the curve is zero. Data is consistent.

Energy change accompanies all chemical reactions. Because of this energy

change the temperature of the products may increase or decrease depending on the

exothermic or endothermic nature of the reaction. The energy change may be

expressed in terms of heat of reaction, heat of combustion and heat of formation.

Heat of reaction is the change in enthalpy of a reaction under pressure of 1.0

atmosphere, starting & ending with all materials at a constant temperature T

Heat of combustion is the heat of reaction of a combustion reaction.

Heat of formation is the heat of reaction of a formation reaction. A formation

reaction is one which results in the formation of one mole of a compound from the

elements.

Eq.

H2 + O2 H2O

C +O2 CO2

C + H2 + 1/2 Cl2 CHCl3

The standard heat of reaction, standard heat of formation, and standard heat of

formation are respectively the heat of reaction, heat of combustion and heat of formation

under 1 atmosphere starting and ending with all materials at constant temperature of

250C.

In chemical industries, processes are carried out under isothermal conditions

and this requires the addition or removal of heat from the reactor. Heat of reaction

values will give the amount of heat to be removed or added. Knowing of this heat

value helps to design the heat exchange equipment.

Standard heat of reaction

Calculation of H298 form heats of formation data:

The standard heat of reaction accompanying any chemical change is equal to

the algebraic sum of the standard heats of formation of products minus the

algebraic sum of the standard heat of formation of reactants.

Hr = Hf 298 products - Hf 298 reactants

Heat of formation of any clement is zero

aA + bB cC + dD

CpB = B + BT + BT2

CpC = C + CT + CT2

CpD = D + DT + DT2

And H0298 be standard heat of reaction at 298 K and standard heat of reaction at any

other temperature can be found by Kirchoffs rule

Cp

Cp

products

d H o

dT

where

Cp

reac tan ts

pC

pD

pA

pB

BT2 )]

= [(c C +d D ) (a A + b B ) ]+ [ (c C + d DT) (a A + b B)]T + [ c C + dD )

(a A+ b B )] T2

or

Cp = + T + T2

Pr oducts

Re ac tan ts

Pr oducts

Pr oducts

Re ac tan ts

Re ac tan ts

H 0 T T T 2

H 0

H298

d

H 0

dT

H o T

T T

2

298

2 3

T

T I

2

3

H o T

OR in general

2 3

T

T I

2

3

H 0 CP dT

=T

T T dT

2

2 3

T

T I

2

3

A chemical reaction proceeds in the direction of decreasing free energy.The sum of the

free energies of the reactants should be more than the sum of energies of products. For a

reaction to take place

GRe action

products

or GRe action 0

reaction

Therefore G should be less than zero for a reaction to occur. When equilibrium is

reached free energies of the reactants equal free energies of products,. Therefore the

criterion for reaction equilibrium is G = 0

GReaction Calculation: Consider the reaction

Let

aA + bB cC + dD

reaction mixture.

GA GA0 RT ln

fA

f

0

A

but

fA

fA0

aA the activity of A

GA GA0 RT lnaA

GB GB0 RT lnaB

GC GC0 RT lnaC

GD GD0 RT lnaD

GRe action

products

Re ac tan ts

cGC dG D aGA bG B

RT

GRe action

lna

ac ad

At equilibrium G = 0 and K Ca Db

a a

A B

ac ad

D

0 G RT ln C

a

a ab

A

B

ac ad

D

G RT ln C

a

a ab

A

B

G0 RT ln K at equilibrium

Gibbs

Helmoholtz

equation

at

constant

pressure

is

given

G o

d

T H

2 but G o RT ln K

dT

T

RT

ln

K

d R ln K H

T

H

2 or

2

dT

dT

T

T

d ln K

H

dT

RT 2

This may be integrated to find the effect of temperature on K

K2

T2

K1

T1

d lnK RT

When H is contant

dT

K2

H 1 1

K1

R T2 T1

if K1 is known at T1 , then K 2 can be calculated at other T2

ln

d ln K

H 0

dT

RT 2

I

T

d ln K

dT

2

RT 2R 3R RT

ln K =

ln T T T 2

I

M

R

2R

6R

RT

G 0 RT ln K

ln T T T 2

I

G 0 RT

M

R

2R

6R

RT

2

3

T

T

G 0 T ln T

I MRT

2

6

For the reasction C2H4 + O2 C2H4O, develop equations for H0, K, and G0, find

G0 at 550 K

Cp (Cal / mol K) Data:

C2H4

= 3.68 + 0.0224 T

O2

= 6.39 + 0.0021 T

H0298

C2H4O = - 12 190 and C2H4

G0298 = -19070 Cal / mol

And

H Re action

298

Pr oducts

Re ac tan ts

In this problem Cp T

Pr oducts

Re ac tan ts

2

Pr oducts

1

2

Re ac tan ts

2 3

0.00975 2

T T I 5.285 T

T I

2

3

2

0.00975 2

0

Given H298

=310 = 5.285 T

T I

then I = 1452

2

0.00975 2

0

H o 5.285T

T 1452

This is variation of H298

with temparature

2

I

5.285

0.00975

1452

lnK =

ln T T T 2

M =

ln T

T

M

R

2R

6R

RT

2

2(2)

2T

H o T

G0298

19070

but G RT ln K 298

or lnK 298

32

RT

2(298)

5.285

0.00975

1452

32 =

ln 298

298

M

therefore M = 48.763

2

2(2)

2(298)

5.285

0.00975

1452

lnK =

ln T

T

48.763

2

4

2T

G0 RT ln K 2T ln K

0

298

0.00975

1452

5.285

2T ln K 2T

ln T

T

48.763

4

2T

2

0

3

2

G 5.285T ln T 4.875(10 )(T ) 1452 97.526(T )

G0550 5.285(550)ln550 4.875(10 3 )(550)2 1452 97 .526(550)

G0550 35320.62 Cal / mol

Show the variation of

298 K are

Hf

Gf

SO2

O2

SO3

mol

mol

-70960

-71680

-94450

-88590

CP data:

Component a

b(103)

SO2

7.116

9.512

O2

6.148

3.102

SO3

6.0377 23.537

Feed contains 50 mole% SO2 and O2.This means for every one mole SO2 there will be

one mole O2 in the reactant side and mole O2 in the product side, according to SO2 +

O2 SO3

Reactants: 1 mol SO2 + 1 mol O2

Pr oducts

reac tan ts

= 6.0377 +

1

6.148 7.116 6.148 - 4.152

2

1

= 23.53(10-3 ) + 3.102(10 3 ) - 9.512 (10 -3 ) + 3.102 (10-3 ) =12.474 x10 -3

2

Pr oducts

reac tan ts

2 3

0

H T

T

T I

2

3

12.474x10 -3 2

= -4.152T+

T I

2

0

But H 0 at 298 is given by H 298

H 0 H 0 94450 70960 23490 k Cal / k mol

products

Re ac tan ts

I = -22818.19

-3

Next for K we have

I

lnK=

ln T

T

T

M

R

2R

6R

RT

4.152

12.474 x10 3

22818.19

lnK=

ln T

T

M

2

2 xR

2T

We have

G0298 =

Products

lnK 298 =

G -

or lnK 298 =

G0298

2(298)

Reactants

16910

28.372

2(298)

4.152

12474 x10 3

22818.19

ln 298

298

M

2

2x 2

2 x 298

M 0.9842

28.372

11409.09

0.9842

T

Derive the general equation for the standard free energy formation for N 2 + 3/2

H2 NH3

The absolute entropies in ideal gas state at 298 K and 1.0 atm are

NH3 = 46.01 g Cal / g mol K

298

N2

= 45.77

H2

= 31.21

Component

bx102

cx105

NH3

6.505

0.613

0.236

N2

6.903

- 0.038

0.193

H2

6.952

- 0.46

0.096

Pr oducts

G0298

Re ac tan ts

3

1

2

2

3

1

2

2

Pr oducts

Re ac tan ts

3

1

2

2

Pr oducts

Re ac tan ts

a

Pr oducts

Re ac tan ts

3

1

2

2

b 2 c 3

0

H298

aT

T

T I

2

3

7.01X 10 3

0.045 X 10 6

11040 ( 7.3745)298

298 2

( 298)3 I

2

3

a

b

c 2

I

ln K

ln T

T

T

M

and R =2 gCal / g mol K

R

2R

6R

RT

0

G298

RT ln K 298

6.6784

or ln K 298 =

OR

I = -9153.26

-3980.38

= 6.6784

-(2x298)

7.3745

7.01x10 3

0.045 x10 6

9153.26

ln 298

298

(298)2

M

2

2x 2

6x2

2 x 298

M 11.7987

-7.3745

7.01x10 3

0.045 x10 6 2 9153.26

G 0 = -2T

ln T

T

T

11.7987

2x 2

6x2

2T

2

3

6

-7.3745

7.01x10

0.045 x10

9153.26

0

G1500

= -2x1500

ln1500

1500

1500 2

11.7987

2x 2

6x2

2x1500

2

0

G1500

Pr oducts

G 28488.81

Re ac tan ts

g Cal

g mol

The reaction is not feasible G is highly +ve: For feasibility it should equal to zero

Temperature 0C

145

6.8 x 10-2

Equilibrium Constant

320

1.9 x 10-3

Component a

bx103

C2H4

2.83

28.601

H2O

7.3

2.46

C2H5OH

6.99

39.741

Develop general expression for the equilibrium constant and standard Gibbs free

energy change as function of temperature.

a

Pr oducts

Pr oducts

lnK =

Re ac tan ts

Re ac tan ts

a

b

c 2

I

ln T

T

T

M

R

2R

6R

RT

3.14

8.68 x10 3

I

ln T

T

M

2

2x 2

2T

3.14

8.68 x10 3

I

At 418 K, ln 6.8x10 -2 =

ln 418

418

M

2

2x 2

2 x 418

3

3.14

8.68 x10

I

At 593 K, ln 1.9x10 -3

ln 593

593

M

2

2x 2

2 x 593

lnK =

3.14

8.68 x10 3

-9655.807

ln T

T

-5.667

2

2x 2

2T

3.14

8.68 x10 3

-9655.807

But G = -2T

ln T

T

-5.667

2

2

x

2

2

T

lnK =

The equilibrium constant K is a measure of the concentration of the products

formed at equilibrium. It is related by the equation G 0 = - RT ln K. The more the value

of K, more will be the equilibrium conversion of products. When the value of G < 0,

means the value of K should be very large. Hence G is the measure of feasibility of a

chemical reaction.

i)

The more the ve value, more will be the feasibility of the reaction

If G0 is +ve but less than 10 000 k Cal / mol, the reaction is not feasible,

ii)

If G0 is greater than 10 000 kCal / mol the reaction is not at all feasible

iii)

Equilibrium Calculations ( Homogeneous gas Phase reactions):

aA (g) + bB (g) cC (g) + dD (g)

ac ad

We have K Ca Db

a a

A B

for gases,

f

E as f 0 = p = 1 atmosphere: a = f

f0

but ac fc x p = c y c c p

Activity a

fc = c y c c

aD D yDD p

a A A y A A p

aB B yB B p

c yc c p D yDD p

a

b

A y A A p B yBB p

c

K=

c D

a

b

A B

c

y c yD

a

b

y A yB

c

c D

a

b

A B

c

p p

a

b

p p

c

y = mole fraction

P = Total pressure

0

RT ln K298 since G depends only on temperature as the

Effect of temperature: G298

pressure is fixed at 1.0 atmosphere, K value varies with temperature. It is not affected by

Pressure,

d ln K

dT

Concentration,

H

RT 2

etc,.

Variation

of

with

is

given

by

means that the equilibrium conversion is more at higher pressure.

For exothermic reactions H0 is ve. Therefore K increases with T. Hence the

equilibrium conversion decreases as T increases. Eg. SO 2 + 1/2 O2 SO3

Effect of pressure: Consider a reaction of ideal gases, then K = KyPn or Ky = K / Pn

yield is less at high pressures

When n< 0.

yield

C2H4 + H2O C2H5OH

N2 + 3H2 2NH3

n = 2 4 = 2

pressure is required

When n = 0 Here pressure has no effect on reaction. For ideal gases the effect

of pressure depends on the variation of and with pressure

Effect of Inert: Presence of inert has the opposite effect of increase of pressure.

Therefore when n

conversion

And n < 0, addition of inert decreases equilibrium conversion.

Effect of excess reactants: Presence of excess reactants increases equilibrium

conversion of the limiting reactant

Presence of products in feed: decreases the equilibrium conversion of reactants.

Eg. CH3COOH + C2H5OH CH3COOC2H5 + H2O

If water is added by 1.0 mole to the feed, equilibrium conversion of CH 3COOH

reduces from 30% to 15%

HCN is produced by the reaction N2 (g)+ C2H2 (g) 2HCN (g). The reactants are

taken in stoichiometric ratio at 1.0 atmosphere and 3000C. At this temperature G0 = 30100

and

n=2 (1+1) = 0

we have G0 RT ln K or lnK =

or K = 1.8029x103

Moles

Moles

Moles

Mole

in feed

reacted

present

fraction

N2

1X

(1 X) / 2

C2H2

1X

(1 X) / 2

HCN

--

2X

2X

Component

K K K y K P n

30100

8.314(573)

(2X) / X =

X

Assume K K 1 and P n P 0 1

K 1.8029(10)3 K y

2

y HCN

y N1 2 yC1 2H2

X2

1 X 1 X

2 2

Equilibrium Composition:

1 X

1 0.0207

N2

100

100 48.965%

2

2

1 X

1 0.0207

C2 H2

100

100 48.965%

2

2

Equilibrium Conversion of C2 H 2

Equilibrium conversion is max imum for reversible reaction

Moles of C2 H2 reacted

X

0.0207

Max. Conversion of C2 H2

100 100

100 2.07%

Moles of C2 H2 in feed

1

1

Workout the problem, when the pressure is changed to 203 bar. Fugacity co efficients

of N2,,C2H2 and HCN are 1.1, 0.928, and 0.54 Assume K= 1

c

K K K y K P n = (1) a C b

A B

y Cc

a b

yA yB

0

203 where a,b, and c are stoichiometric co efficients

0.542

X2

and K is known already = 1.8029x10 -3 =

.(1)

2 2

solving X = 0.0382

then equilibrium Composion of C2H2 is ( Max reversible reaction)

moles C2 H2 reacted

0.0382

=

x 100 = 3.82%

moles of C2 H2 in feed

1

Calculate the K at 673K & 1.0 bar for N2 (g) + 3 H2 (g) 2NH3 (g).

Assume heat of reaction remains constant. Take standard heat of formation and

standard free energy of formation of NH3 at 298 K to be - 46110 J / mol and 16450 J

/ mol respectively.

0

G298

2( 16450) 32900 J

0

H298 2 (-46110) = -92 220 J

0

G298

RT ln K 298

0

G298

RT ln K1

K1 564861.1

K2

H 1

1

K1

R T2 T1

K2

92220 1

1

ln

584861.1

8.314 673 298

0

we have ln

K 2 5.75 X 10 4

Acetic acid is esterified in the liquid phase with ethanol at 373 K and 1.0 bar according

to

CH3COOH (L) + C2H5OH (L) CH3COOC2H5(L) + H2O (L)

The feed consists of 1.0 mol each of acetic acid & ethanol, estimate the mole fraction of

ethyl acetate in the reacting mixture at equilibrium. The standard heat of formation

and standard free energy of formation at 298 K are given below.

Assume that the heat of reaction is independent of T and liquid mixture behaves as

ideal solution.

f0f

(J)

G0f

(J)

CH3COOH

C2H5OH

(L)

(L)

- 484500

- 277690

- 463250

- 285830

- 389900

-174780

- 318218

- 237130

H0298 = 463250 285830 + 277690 + 484500 = 13110 J

We have, G0298 = RT ln K

9332 = 8.314 (298) ln K1

or K1 = 0.02313

K1

H 1

1

K2

R T1 T2

0.02313

12110 1

1

ln

K2

8.314 298 373

ln

OR K 2 0.067

Moles

Moles

Moles

Mole

in feed

reacted

present

fraction

CH3COOH

1X

(1 X) / 2

C2H5OH

1X

(1 X) / 2

CH3COOC2H5 --

X/2

H2O

X/2

Component

--

K2 K y P 0

0.067=

x

2

1 x

2

x2

(1 x )2

solving, x = 0.252

x 0.252

0.126

2

2

The standard free energy change for the reaction C4H8 (g) C4H6 (g) + H2 (g)

is given by GT0 =1.03665 X 105 20.9759T ln T 12.9372 T, where range of GT0 in J

/ mol and T in K

a) Over what range of T, is the reaction promising from thermodynamic view

point?

b) For a reaction of pure butene at 800K, calculate equilibrium conversion at 1.0

bar & 5.0 bar

c) Repeat part (b) for the feed with the 50 mol% butene and the rest inerts

a.

At 800K, G0 = 1842.16 J / mol

b.

G0 = - RT ln K,

or

or

K = 1.3191

K = ky Pn = ky P ( 2- 1 ) = ky P

Therefore

ky = 1.31910At 5 bar,

1.3191 = ky ( 1 )

1.3191 = ky ( 5 )

ky = 0.26382

Moles

feed

C4H8

yi

(1 X ) / (1 +

1-X

X)

C4H6

X / (1 + X)

H2

X / (1 + X)

1+X

kY

'

C4 H 6

'

H2

YC' 4H8

x x

1 x 1 x

1 x

1 x

or 1.3191 =

x2

or

1 x2

x = 0.7541

At 5.0 bar, k y = 0.26382 =

x2

,

1 x2

C.

Moles

feed

C4H8

C4H6

yi

1-X

(1 X ) / (2 + X)

X / (2 + X)

H2

Inerts

1.0

X / (2 + X)

1 / (2 + X)

2+x

at 1.0 bar,

k Y K 1.3191

x2

2 x

2x

1 x

x = 0.8194

at 5.0 bar

kY

K

x2 2 x

0.26382

2

5

2 x 1 x

x = 0.5501

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